Process for preparation of fast dyeings of prints on synthetic fiber materials

ABSTRACT

A process for the preparation of fast dyeings or prints on synthetic fibrous materials which comprises treating the said fibrous materials in aqueous dispersion or in an organic solvent with dyestuffs of the formula IN WHICH R1 represents alkyl from one to four carbon atoms being unsubstituted or substituted by methoxy or ethoxy, and R2 represents phenyl being unsubstituted or substituted by fluorine, chlorine, bromine, alkyl or one to four carbon atoms, alkoxy of one to four carbon atoms, trifluoro-methyl, nitro, hydroxy, cyano, carbo(lower)alkoxy, acetyl, benzoyl, phenyl or phenoxy, the yellow dyeings or prints so obtained being distinguished by excellent fastness properties, particularly by a very good fastness to light and a high fastness to sublimation.

United States Patent Brenneisen et al.

[ PROCESS FOR PREPARATION OF FAST DYEINGS OF PRINTS ON SYNTHETIC FIBERMATERIALS [75] Inventors: Erich Brenneisen, l-lofheim/Taunus;

Ernst I-Ioyer, Frankfurt/Main; Maria Kallay, Mammolshain/Taunus;KarHIeinz Krell, Kronberg/Taunus; Willi Steckelberg, l-Iofheim/Taunus,all of Germany [73] Assignee: Farbwerke Hoechst Aktiengesellschaftvormals Meister Lucius & Bruning, Frankfurt, Germany 22 Filed: Feb. 22,1973 21 7 App]. No.: 334,836

[30] Foreign Application Priority Data Feb. 26, 1972 Germany 2209209[52] US. Cl. 8/41 C, 8/41 R, 8/71,

8/94, 260/193 [51] Int. Cl. D06p 3/60, C09b 29/32 [58] Field of Search.8/4-1 R, 41 C, 71, 94; 260/193 [56] References Cited UNITED STATESPATENTS 2,211,339 8/1940 McNally et al. 260/193 FOREIGN PATENTS ORAPPLICATIONS 407,368 8/1966 Switzerland 260/193 [451 Feb. 19, 1974Primary Examiner Donald Levy Assistant Examiner-Bruce H. Hess Attorney,Agent, or Firm-Curtis, Morris & Safford [57] ABSTRACT A process for thepreparation of fast dyeings or prints on synthetic fibrous materialswhich comprises treating the said fibrous materials in aqueousdispersion or in an organic solvent with dyestuffs of the formula N02 IA to 11 Claims, N0 Drawings PROCESS FOR PREPARATION OF FAST DYEINGS OFPRINTS ON SYNTHETIC FIBER MATERIALS The present invention relates to aprocess for the preparation of fast dyeings or prints on synthetic fibermaterials, wherein said fiber materials are treated with dyestuffs ofthe general formula (1) in which R, represents an alkyl group having oneto four carbon atoms which may be substituted by a methoxy or ethoxygroup, and R stands for a naphthyl radical or a phenyl radical which maybe substituted by a halogen atom, an alkyl and/or alkoxy group, eachhaving one to four carbon atoms, a trifluoromethyl, nitro, hydroxy,cyano, carbalkoxy, acetyl, benzoyl, phenyl and/or phenoxy group in anaquous dispersion or in an organic solvent.

Dyestuffs of the general formula (2) (IJN for example in a solution orsuspension of a mineral acid with nitrite and coupling with a couplingcomponent of the general formula (5), preferably of the general formula(6) for example in a weakly alkaline, neutral or acid solution orsuspension.

In the above formulae (3), (5) and (6), R R and A are defined as above.

As synthetic fiber materials, there are mentioned, for example, fibersmade from cellulose esters, polyesters, polyamides, polyurethanes,polyolefins and polyacrylonitriles, preferably cellulose esters, such ascellulose acetate and cellulose triacetate; especially fibers made frompolyesters, such as polyethylene terephthalate. The synthetic fibermaterials may also be blended with each other or with natural fibrousmaterials, such as cellulose fibers or wool. These materials mayfurthermore be dyed or printed in various processing forms, for exampleas combed material, flakes, filaments, knit or woven fabrics.

The dyestuffs used according to the invention are applied, on principlein known manner, generally from an aqueous dispersion but also from anorganic solvent. The dyestuffs may be dispersed, for example by grindingthem in the presence of a dispersing agent, such as a condensationproduct of formaldehyde and a naphthalene-sulfonic acid.

Otherwise, the dyeing conditions depend, to a large extent, on the typeof synthetic fiber materials and their processing form.

For example, shaped articles made of cellulose acetate are dyed at atemperature ranging from about to about C, whereas cellulose triacetatefibers are dyed at a temperature of from about to about C.

As to a polyamide fiber material, the dyestuffs are applied at atemperature of from about 90 to about 120C. Polyester fiber materialsare dyed according to known methods in the presence of carriers, such asortho or para-phenyl-phenol, methyl-naphthalene or methyl-salicylate, ata temperature of about 100 to about C, or in the absence of carriers athigher temperatures, for example between 120 and about C. Moreover,according to the present process, the dyestuffs may also be applied tothe said fibrous materials by pad-dyeing with or without a thickeningagent, for example, a tragacanth thickener, and fixed under the actionof heat, for example, by means of vapor or dry heat over about half aminute to 30 minutes at a temperature of from about 100 to about 230C.In order to improve the fastness to rubbing, the material thus dyed isthen freed from dyestuff adhering to its surface, for example, bywashing or subjecting it to a reductive after-treatment. This reductiveaftertreatment is generally performed at about 60 to about 120C in aliquor containing an aqueous sodium hydroxide solution, sodiumdithionite and a non ionic detergent, for example an addition product ofethylene oxide and phenol.

For the dyeing of synthetic fiber materials from organic solvents, thedyestuff may, for example, be allowed to be absorbed by the fiber fromthe solution at room temperature or at an elevated temperature,preferably at about 70 to about 130C, where required under pressure, ora knit or woven fabric may be impregnated in a continuous operation witha dyestuff solution, dried and exposed to heat for a short time, forexample at a temperature of from about 180 to about 210C.

As solvents to be used for the exhaustion method, there may, forexample, be mentioned solvents which are not miscible with water andhave boiling points of about 40 to about C, such as aliphatichalogenated hydrocarbons, for example methylene chloride,trichloro-ethane, trichloro-ethylene, perchloroethylene ortrifluoro-trichloroethane. For a continuous dyeing operation, there mayespecially be used water-miscible solvents, for example alcohols ordimethylformamide. The solvents may, of course, also be used in mixturewith each other and may contain further adjuvants which are soluble insolvents, for example oxyalkylation products of fatty alcohols,alkyl-phenols and fatty acids.

For the production of prints on synthetic fiber materials, for examplethose made from polyesters, polyamides or cellulose triacetate, thedyestuffs to be used according to the invention may be applied in theform of aqueous compositions which may contain suitable thickeners andfixation-promoting agents in addition to the finely divided dyestuffs.Fixation is performed, for example after printing and drying, by meansof steaming under atmospheric pressure or under elevated pressure of upto 2.5 atmospheres gage over to 60 minutes. Fixation may also be broughtabout by the action of hot air of about 160 to about 210C for a periodof 30 seconds to 10 minutes.

The novel dyestuffs to be used according to the invention afford yellowdyeings and prints having excellent fastness properties. The dyeings andprints obtained by the present process are particularly distinguished byvery good fastnesses to light and very good dyestuff yields, and also bya high fastness to sublimation.

As against dyeings and prints which may be obtained with the nextcomparable dyestuffs disclosed in US. Pat. Specification No. 2.21 1.339and Swiss Pat. Specification No. 407 368, the dyeings and printsobtained according to the process of the present invention have superiorproperties, particularly a better affinity on polyester fiber materialsand better properties of fastness such as fastness to light andthermofixation.

The following examples illustrate the invention, the parts andpercentages being by weight unless stated otherwise, the parts by volumeare to' the parts by weight as liter to kilogram under normalconditions.

EXAMPLE 1 10 Parts of polyester fabric were introduced into a dye-bathheated to 50C and containing 400 parts of softened water and 0.2 part ofthe dyestuff of formula in finely divided form.

The pH-value of the dyebath was adusted to 5-5.5 by means of ammoniumsulfate and acetic acid. Within 40 to 60 minutes, the temperature wasraised to 130C and the material was then dyed for 1 hour at thistemperature.

The fabric was then taken out of the bath, rinsed and subjected to areductive after-treatment for minutes at 80 to 90C in a bath containing,per liter, six parts of sodium hydroxide solution (38 Be), four parts ofsodium dithionite and one part of a non-ionic detergent. The dyed fabricwas finally rinsed and dried.

A yellow dyeing having outstanding properties of fastness was obtained,especially an excellent fastness to light and a high tinctorialstrength.

Similar results were obtained when using instead of a polyester fabric afabric of cellulose triacetate and carrying out the dyeing at 110C.

Dyeings having the same good properties of fastness were also obtainedby dyeing polyester yarn for 30 minutes at 120C in a closed apparatuswith the dyestuff of the formula (7) from perchloroethylene.

The dyestuff of the aforementioned formula (7) was obtained as follows:

33.6 parts of 3-nitro-4-amino-anisole were dissolved in the heat in 400parts of water and 120 parts of 5N- hydrochloric acid and, after pouringonto 2,000 parts of ice water, diazotized with 40 parts by volume of a5N sodium nitrite solution.

40.8 parts of the coupling component 2-chlorocyanoacet-anilide weredissolved at room temperature in 800 parts of water and 54 parts ofcolume of a 33 percent aqueous sodium hydroxide solution and, afteradding two parts of a non-ionic emulsifier such as the reaction productof oleyl alcohol and 30 mols of ethylene oxide, precipitated in finelydivided form, while stirring, by rapidly adding 40 parts by volume ofglacial acetic avoid.

The diazo solution was then added and the pl-l-value was adjusted toabout 6.5 by means of sodium hydroxide solution.

The precipitated dyestuff was isolated by filtration and washing. Itcould be dried or brought into a finely divided dispersion, in the formof the aqueous filter residue and by means of a commercial dispersingagent, for example a condensation product of formaldehyde and anaphthalene-sulfonic acid.

EXAMPLE 2 10 Parts of polyester yarn were introduced into a dyebathheated to 60C and containing 300 parts of softened water, 0.3 part ofthe finely divided dyestuff of the formula (8) one part of a commercialcarrier, for example 0- phenylphenol, and 0.5 part of ammonium sulfate.

The pH-value of the dyebath was adjusted to 5 to 5.5 by means of aceticacid. Within 30 to 60 minutes, the temperature was raised to boilingtemperature and the material was dyed for minutes at this temperature.

The dyed material was then after-treated and finished as described inExample 1.

In this manner reddish yellow dyeings were obtained which possessed verygood properties of fastness and a high color yield.

The dyestuff of the formula (8) was obtained by using as couplingcomponent 35.9 parts of 4-hydroxycyanoacet-anilide and proceedingotherwise as described in Example (1).

EXAMPLE 3 A mixed fabric of polyester and cellulose was impregnated at25 to 30C with a dyeing liquor the pH value of which was adjusted to 5to 5.5 by means of acetic acid and which contained the finely divideddyestuff of the formula (9).

The material was then dried at a temperature of from 100 to 110C.Fixation was brought about by dry heat for 30 to 90 seconds at 190 to230C. Finally, the fabric was subjected to a reductive after-treatmentas described in Example 1 and finished.

An intense yellow dyeing having excellent properties of fastness,especially a very good fastness to light, was obtained. Similarhigh-quality dyeings were obtained by dyeing cellulose triacetate fibermaterials in the same manner.

The dyestuff of the formula (9) was obtained using as coupling component49.5 parts of 2-chloro-4-nitrocyanoacet-anilide and otherwise followingthe treatment as disclosed in Example 1.

EXAMPLE 4 A polyester fabric was printed with a printing pastecontaining, per 1,000 parts, in addition to a commercial thickener, suchas alginate and starch ether, as well as further usual additives, 200parts of an aqueous dyestuff composition containing percent of thefinely divided dyestuff of the formula (10) and then dried.

The dyestuff was then fixed for 60 seconds at 200C by hot air.

The print was rinsed, subjected to a reductive aftertreatment in a bathcontaining sodium dithionite and sodium hydroxide solution, then cleanedagain in another bath containing a non-ionic detergent, for example thecondensation product of nonylphenol and 10 mols of ethylene oxide,rinsed again and dried.

A yellow print having a high color intensity and excellent properties offastness, particularly an outstanding fastness to thermofixation andlight, was obtained. Similar good results were obtained by carrying outthe fixation for minutes by means of pressurized steam of 2 atmospheresgage.

When, instead of a polyester fabric, a fabric of cellulose triacetatewas used, for which no reductive aftertreatment was necessary,color-intense prints having very good fastness properties were likewiseobtained.

The dyestuff of the formula (10) was obtained by using as couplingcomponent 44.5 parts of 3-carbomethoxy-cyanoacetanilide and otherwisefollowing the treatment disclosed in Example 1.

EXAMPLE 5 N02 on;

and then dried.

The fixation was carried out by steaming under atmospheric pressure for30 minutes.

After cleaning and drying, a yellow print having a high color intensityand good fastness properties was obtained.

Valuable prints were also obtained using, instead of to be usedaccording to the invention.

Ex. R R Shade on No. polyester fibers 6 CH 3'trifluoromethyl-phenylyellow 7 CH Z-bromo-phenyl yellow 8 CH, 4-t-butylphenyl yellow 9 CH2-nitro-phenyl yellow 10 Cl-l 2,4-dinitro'phenyl yellow 11 CH4-nitro-2,-dichloro-phenyl yellow 12 CH, 4-methoxy-phenyl yellow 13 CH;a-naphthyl reddish yellow 14 CH; 3-benzoyl-phenyl yellow 15 CH 2phenoxyphenyl yellow 16 CH: 4-bisphenyl yellow 17 C H 4-chloro-phenylyellow 18 C l-l 2 chloro-4-nitro-phenyl yellow 19 C H 4-hydroxy phenylreddish yellow 20 C H 4-i-propyl-phenyl yellow 21 C H 4-n-butoxy-phenylyellow 22 C H 4-hydroxy-phenyl reddish yellow 24 C3H7 4ethoxy-phenylyellow 25 n-C H 2,4,5-trichloro-phenyl yellow 26 n-C H phenyl yellow 27'C4Hg 4-hydroxy-phenyl reddish yellow 28 n-C H 3 acetyl'phenyl yellow 29n-C H 4-ethyl-phenyl yellow 30 CH;,OC H yellow 2-chloro-phcnyl 31 CH OCH reddish yellow 4-methoxy-phenyl 32 CH OC H yellow 3-cyan0-phcnyl 33 CHOC H reddish yellow 4hydroxy-phenyl 34 CH OC H yellow2-chloro-4nitro-phenyl 35 C H OC H reddish yellow 4-hydroxy-phenyl 36 CH OC H 2-nitro4-trifluoro-methyl-phenyl yellow We claim:

1. A process for the preparation of fast dyein gs or prints on syntheticfibrous materials which comprises treating the said fibrous materials ina dye bath selected from the group consisting of an aqueous dispersion,an organic solvent and mixtures thereof with a dyestuff of the formulain which R represents alkyl from one to four carbon atoms beingunsubstituted or substituted by methoxy or ethoxy, and R representsphenyl being unsubstituted or substituted by fluorine, chlorine,bromine, alkyl of one to four carbon atoms, alkoxy of one to four carbonatoms, trifluoromethyl, nitro, hydroxy, cyano, carbo(- lower)alkoxy,acetyl, benzoyl, phenyl or phenoxy, or combinations of two or threemembers thereof, or naphthyl.

2. A process as claimed in claim 1, wherein the synthetic fibrousmaterials consist of celluloseacetate or polyester.

3. A process as claimed in claim 1, wherein the said fibrous materialsare dyed with an aqueous dispersion of the said dyestuffs between about75C and about 140C in the absence or in the presence of a carrier.

4. A process as claimed in claim 1, wherein the said fibrous materialsare dyed with the said dyestuffs from organic solvents between roomtemperature and about l30C.

5. A process as claimed in claim 1, wherein the said fibrous materialsare padded with an aqueous dispersions of the said dyestuffs and thedyestuffs are subsequently fixed at elevated temperature.

6. A process as claimed in claim 5, wherein the aqueous dispersion ofthe dyestuffs contains a thickening agent.

7. A process as claimed in claim 5, wherein the dyestuffs are fixed bysteaming or treating them with dry heat at a temperature between about100 and about 230C.

8. A process as claimed in claim 1, wherein the fibrous materials areimpregnated with the said dyestuffs from an organic solvent and dried,and the dyestuffs are subsequently fixed by a short-time action of heat.

9. A process as claimed in claim 1, wherein the dyestuffs are fixed by ashort-time action of heat at a temperature of from about C to about210C.

10. A process as claimed in claim 1, wherein the said fibrous materialsare printed with water-containing preparations of the said dyestuffs andthe dyestuffs are subsequently fixed by drying the prints and steamingthem under atmospheric pressure or elevated pressure of up to 2.5 atmgor by a short-time action of hot air of about 180C to about 210C.

11. A process as claimed in claim 10, wherein the water-containingpreparations of the dyestuffs contain a member selected from the groupconsisting of a thickening agent, a fixing accelerator and a combinationthereof.

2. A process as claimed in claim 1, wherein the synthetic fibrousmaterials consist of celluloseacetate or polyester.
 3. A process asclaimed in claim 1, wherein the said fibrous materials are dyed with anaqueous dispersion of the said dyestuffs between about 75*C and about140*C in the absence or in the presence of a carrier.
 4. A process asclaimed in claim 1, wherein the said fibrous materials are dyed with thesaid dyestuffs from organic solvents between room temperature and about130*C.
 5. A process as claimed in claim 1, wherein the said fibrousmaterials are padded with an aqueous dispersions of the said dyestuffsand the dyestuffs are subsequently fixed at elevated temperature.
 6. Aprocess as claimed in claim 5, wherein the aqueous dispersion of thedyestuffs contains a thickening agent.
 7. A process as claimed in claim5, wherein the dyestuffs are fixed by steaming or treating them with dryheat at a temperature between about 100* and about 230*C.
 8. A processas claimed in claim 1, wherein the fibrous materials are impregnatedwith the said dyestuffs from an organic solvent and dried, and thedyestuffs are subsequently fixed by a short-time action oF heat.
 9. Aprocess as claimed in claim 1, wherein the dyestuffs are fixed by ashort-time action of heat at a temperature of from about 180*C to about210*C.
 10. A process as claimed in claim 1, wherein the said fibrousmaterials are printed with water-containing preparations of the saiddyestuffs and the dyestuffs are subsequently fixed by drying the printsand steaming them under atmospheric pressure or elevated pressure of upto 2.5 atmg or by a short-time action of hot air of about 180*C to about210*C.
 11. A process as claimed in claim 10, wherein thewater-containing preparations of the dyestuffs contain a member selectedfrom the group consisting of a thickening agent, a fixing acceleratorand a combination thereof.